CN109280265A - A kind of preparation method of low odor scratch-resistant PP composite material - Google Patents
A kind of preparation method of low odor scratch-resistant PP composite material Download PDFInfo
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- CN109280265A CN109280265A CN201811015027.2A CN201811015027A CN109280265A CN 109280265 A CN109280265 A CN 109280265A CN 201811015027 A CN201811015027 A CN 201811015027A CN 109280265 A CN109280265 A CN 109280265A
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- resistant
- scratch
- composite material
- low odor
- polypropylene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of preparation methods of low odor scratch-resistant PP composite material, belong to technical field of rubber material.The present invention provides basic framework using elastomer, engagement interlocking structure is constituted, and is dispersed in it in polypropylene with three kinds of nano-titanium dioxide, modified wood powder and calcium carbonate inorganic matters, reduces the Plastic Flow of material, and it is able to ascend rigidity, improves scratch-resistant ability;Each component Interface adhesive strength is improved with silane coupling agent and maleic anhydride graft polypropylene, shrinkage factor at late stage can be reduced finally by being impregnated again with warm water after injection molding machine, manufactured low odor scratch-resistant PP composite material has the characteristics that good resistance to compression impact resistance, shrinking percentage is small, smell is low, scratch-resistant, has broad application prospects and market value.
Description
Technical field
The present invention relates to a kind of preparation methods of low odor scratch-resistant PP composite material, belong to rubber material technology neck
Domain.
Background technique
In recent years, due to the fast development of polypropylene material through engineering approaches modification technology, in the application of automotive field
It is more and more extensive.However, an important component as engineering polypropylene material in automotive field, poly- by being engineered
Various automobile interior decoration products made of propylene material, although can meet corresponding requirements in its service performance in all respects,
It is since these materials can all release certain nifves to varying degrees, thus by the more and more matter of consumer
It doubts.Moreover, as people's environmental protection and health awareness constantly enhances, suffered challenge will be got over polypropylene material in this regard
Come more serious.High-crystallinity polypropylene (HCPP) is that a kind of high performance is resin dedicated, and surface hardness is high, and density is small, 0.9-0.91
Gram/cc, isotacticity 98% one 99%, crystallinity has high intensity, high heat resistance, high rigidity, excellent up to 70% or more
The good feature of glossiness, wearability, flexural fatigue resistance, performance is close to engineering plastics.Since HCPP crystallization temperature is higher than commonly
Polypropylene product, therefore the product molding period is substantially shorter, extremely low density in addition, thus be easy to reach the product of manufacture
It is thinning, lightweight.The disadvantage is that shrinking percentage is big, not scratch-resistant relatively.Due to the above many advantages, polypropylene is in vehicular accessory system
Application aspect is made to be more and more favored.
In general, it is believed that the smell of polypropylene material is as caused by the following aspects.Firstly, in polypropylene
Catalyst system used in resin matrix synthesis process contains the compound of the irritant peculiar smell of some bands, such as ester type compound
Or alkane derivative, this kind of compound can not completely remove after resin polymerization completion, they remain in polypropylene tree
In rouge, so that the irritant peculiar smell of polypropylene material band.Secondly, being modified the mistake of processing in PP matrix
Cheng Dangzhong, acrylic resin can more or less generate the low molecular compound of certain degradations in the state of melting, such as ketone, aldehyde
Class compound.These material parts rest in modified material, and stimulation is gradually given out in the use process of product
The smell of property.Again, added some filler components in modified polypropylene material, such as talcum powder, they can equally have certain
A little penetrating odors.Finally, added certain stabilizers are with certain irritation peculiar smell in modified polypropylene material.
PP composite material typically contains certain smell, and it is residual that smell source mainly comes from catalyst in polymerization process
The small molecule chemical combination that thermal-oxidative degradation in the dissolvent residual and process stay, added in monomeric compound production process generates
Object.Cause in-car air quality to decline in this way, seriously affects human body health.State Ministry of Environmental Protection and State Administration of Quality Supervision, Inspection and Quarantine exist thus
Combine in March, 2012 and issued GB/T27630 " Air Quality Evaluation guide in passenger car ", the guide is main empty to interior 8 kinds
The concentration of gas pollutant has made stringent regulation.So polyacrylic odor properties must be improved just can become it is a more
Excellent application material.
Existing solution valuable gases adsorbent, the low VOC pernicious gas of nano photo-catalytic adsorption-decomposition function, and have and kill
Bacterium effect, but nano material common feature is to be easy to reunite, and additional amount is restricted.For this purpose, in order to further expand polypropylene
Application of the material in related fields, it is necessary to search out an effective way to prepare low smell, even scentless polypropylene
Material.
Summary of the invention
The technical problems to be solved by the invention: for for common polypropylene material odorous, scratch-resistant is not asked
Topic, proposes a kind of preparation method of low odor scratch-resistant PP composite material.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
(1) polystyrene, tetrahydrofuran and nano silica are stirred evenly, is put into electrostatic spinning apparatus and carries out spinning, obtains
To electrostatic spinning fiber, fibrous material is obtained for 24 hours in 80 DEG C of dryings;
(2) take wood powder and sodium hydroxide solution that 15min is mixed;
(3) it filters, and filter residue is rinsed with deionized water, rinse 3 ~ 5 times, by filter residue standing and drying, obtain modified wood powder;
(4) take nano-titanium dioxide, modified wood powder, calcium carbonate, EP rubbers, vinyltriethoxysilane and polysiloxanes mixed
It closes and uniformly obtains material A;
(5) polypropylene, dimethyl silicone polymer, maleic anhydride inoculated polypropylene is taken to be mixed to get material B;
(6) it takes material B to feed from twin-screw extrusion owner's spout, material A is taken to feed from side spout, twin-screw extrusion is female
Grain;
(7) master batch is put into 60 DEG C of warm water and stirs 30min, then master batch is filtered out and is put into 80 DEG C of vacuum drying ovens dry 2 ~ 4
Hour, by the master batch after drying by injection molding machine, obtain low odor scratch-resistant PP composite material.
The mass ratio of step (1) polystyrene, tetrahydrofuran and nano silica is 3:6:1.
Step (2) concentration of sodium hydroxide solution is 3mol/L.
Step (4) nano-titanium dioxide, modified wood powder, calcium carbonate, EP rubbers, vinyltriethoxysilane and
The mass ratio of polysiloxanes is 20:20:20:15:1:10.
Step (5) polypropylene, dimethyl silicone polymer, maleic anhydride inoculated polypropylene mass ratio be 100:20:
1。
The mass ratio of step (6) material A and material B are 7:3.
The present invention is compared with other methods, and advantageous effects are:
(1) it is added to fibrous material in the material, provides basic framework for composite material, reduces the stream modeling of composite material
Property, improve scraping and wiping resistance performance;After by wood powder soaking with sodium hydroxide, so that wood powder dispersibility is more preferable, increment composite wood
The toughness of material;Nano-titanium dioxide, modified wood powder and calcium carbonate mix, and three kinds intermolecular to form a kind of engagement interlocking structure,
Improve the shock resistance of composite material;
(2) nano-titanium dioxide can decompose toxic and harmful gas under daylight or ultraviolet light irradiation as photocatalyst, subtract
The peculiar smell of few composite material;
(3) present invention provides basic framework using elastomer, inorganic with nano-titanium dioxide, modified wood powder and three kinds of calcium carbonate
Object constitutes engagement interlocking structure, and is dispersed in it in polypropylene, reduces the Plastic Flow of material, and be able to ascend
Rigidity, improves scratch-resistant ability;Each component interface bonding energy is improved with silane coupling agent and maleic anhydride graft polypropylene
Power can reduce shrinkage factor at late stage, manufactured low odor scratch-resistant polypropylene finally by being impregnated again with warm water after injection molding machine
Composite material has the characteristics that good resistance to compression impact resistance, shrinking percentage is small, smell is low, scratch-resistant.
Specific embodiment
30 ~ 45g polystyrene, 60 ~ 90g tetrahydrofuran and 10 ~ 15g nano-titanium dioxide are stirred evenly, electrostatic is put into
Device for spinning carries out spinning, obtains electrostatic spinning fiber, obtains fibrous material for 24 hours in 80 DEG C of dryings;Take 40 ~ 60g wood powder and
15min is mixed in 200g3mol/L sodium hydroxide solution;Filtering, and filter residue is rinsed with deionized water, rinse 3 ~ 5
It is secondary, by filter residue standing and drying, obtain modified wood powder;Take 20 ~ 30g nano-titanium dioxide, 20 ~ 30g modified wood powder, 20 ~ 30g carbonic acid
Calcium, 15 ~ 20g EP rubbers, 1 ~ 2g vinyltriethoxysilane and 10 ~ 15g polysiloxanes are uniformly mixed and obtain material A;It takes
100 ~ 150g polypropylene, 20 ~ 30g dimethyl silicone polymer, 1 ~ 2g maleic anhydride inoculated polypropylene are mixed to get material B;Take 70 ~
110g material B is fed from twin-screw extrusion owner's spout, and 30 ~ 45g material A is taken to feed from side spout, and twin-screw extrusion is female
Grain;Master batch is put into 60 DEG C of warm water and stirs 15min, then master batch is filtered out to and is put into drying 2 ~ 4 hours in 80 DEG C of vacuum drying ovens,
By the master batch after drying by injection molding machine, low odor scratch-resistant PP composite material is obtained.
30g polystyrene, 60g tetrahydrofuran and 10g nano-titanium dioxide are stirred evenly, be put into electrostatic spinning apparatus into
Row spinning, obtains electrostatic spinning fiber, obtains fibrous material for 24 hours in 80 DEG C of dryings;Take 40g wood powder and 200g3mol/L sodium hydroxide
15min is mixed in solution;Filtering, and filter residue is rinsed with deionized water, it rinses 3 times, filter residue standing and drying obtains
Modified wood powder;Take 20g nano-titanium dioxide, 20g modified wood powder, 20g calcium carbonate, 15g EP rubbers, 1g vinyl triethoxyl
Silane and 10g polysiloxanes, which are uniformly mixed, obtains material A;Take 100g polypropylene, 20g dimethyl silicone polymer, 1g maleic anhydride
Graft polypropylene is mixed to get material B;It takes 70g material B to feed from twin-screw extrusion owner's spout, takes 30g material A from side feed
Material mouth feeding, twin-screw extrusion master batch;Master batch is put into 60 DEG C of warm water and stirs 15min, then master batch is filtered out and is put into 80 DEG C
It is 2 hours dry in vacuum drying oven, by the master batch after drying by injection molding machine, obtain low odor scratch-resistant PP composite material.
37g polystyrene, 75g tetrahydrofuran and 13g nano-titanium dioxide are stirred evenly, be put into electrostatic spinning apparatus into
Row spinning, obtains electrostatic spinning fiber, obtains fibrous material for 24 hours in 80 DEG C of dryings;Take 50g wood powder and 200g3mol/L sodium hydroxide
15min is mixed in solution;Filtering, and filter residue is rinsed with deionized water, it rinses 4 times, filter residue standing and drying obtains
Modified wood powder;Take 25g nano-titanium dioxide, 25g modified wood powder, 25g calcium carbonate, 17g EP rubbers, three ethoxy of 1.5g vinyl
Base silane and 13g polysiloxanes, which are uniformly mixed, obtains material A;Take 125g polypropylene, 25g dimethyl silicone polymer, the Malaysia 1.5g
Anhydride-grafted polypropylene is mixed to get material B;Take 90g material B from twin-screw extrusion owner's spout feed, take 37g material A from
Side spout feeding, twin-screw extrusion master batch;Master batch is put into 60 DEG C of warm water and stirs 15min, then master batch is filtered out and is put into
It is 3 hours dry in 80 DEG C of vacuum drying ovens, by the master batch after drying by injection molding machine, obtain low odor scratch-resistant polypropylene composite materials material
Material.
45g polystyrene, 90g tetrahydrofuran and 15g nano-titanium dioxide are stirred evenly, be put into electrostatic spinning apparatus into
Row spinning, obtains electrostatic spinning fiber, obtains fibrous material for 24 hours in 80 DEG C of dryings;Take 60g wood powder and 200g3mol/L sodium hydroxide
15min is mixed in solution;Filtering, and filter residue is rinsed with deionized water, it rinses 5 times, filter residue standing and drying obtains
Modified wood powder;Take 30g nano-titanium dioxide, 30g modified wood powder, 30g calcium carbonate, 20g EP rubbers, 2g vinyl triethoxyl
Silane and 15g polysiloxanes, which are uniformly mixed, obtains material A;Take 150g polypropylene, 30g dimethyl silicone polymer, 2g maleic anhydride
Graft polypropylene is mixed to get material B;It takes 110g material B to feed from twin-screw extrusion owner's spout, takes 45g material A from side
Spout feeding, twin-screw extrusion master batch;Master batch is put into 60 DEG C of warm water and stirs 15min, then master batch is filtered out and is put into 80
It is 4 hours dry in DEG C vacuum drying oven, by the master batch after drying by injection molding machine, obtain low odor scratch-resistant polypropylene composite materials material
Material.
The polypropylene composite materials that low odor scratch-resistant PP composite material prepared by the present invention and Shandong company are produced
Material is detected, specific testing result such as following table table 1:
Detection method:
Low odor scraping-resistant polypropylene material obtained in above-described embodiment is randomly selected to be tested for the property.
Wherein, the scraping and wiping resistance performance in following test item is according to General Motors Overseas Corporation to automotive upholstery damage resistant mark
Quasi- GMW14688 is tested, i.e., by sample injection molding 60mm × 60mm × 3mm template, scrapes abrasion instrument using the five fingers
It carries out drawing lattice scratch test with the power of 10N or 15N, the severity of scratch is determined with brightness change value Δ L, Δ L is smaller, then
Show that the scraping and wiping resistance performance of material is better.Wherein, the automobile vendors such as AM General and Ford are recognized as meeting the requirements to Δ L≤2;
It wherein, is 1~10 rank by oder levels according to the standard referring to GMW3205 standard to smell testing standard;Wherein,
Rank 1 is expressed as insupportable smell, and rank 10 is expressed as not having smell substantially, is to conform to oder levels rank >=6
It asks;
Tensile strength testing standard therein is referring to national standard GB/T1040, and bending strength test is referring to national standard GB/T9341, cantilever
The test of beam notch impact strength is referring to national standard GB/T1843;The following table 1 is properties test result.
The low odor scratch-resistant type Properties of Polypropylene Composite of table 1 characterization
As shown in Table 1, low odor scratch-resistant type PP composite material prepared by the present invention, tensile strength is high, Scratch Resistance energy
Good, smell is low, and the present invention has good market prospects and application prospect.
Claims (6)
1. a kind of preparation method of low odor scratch-resistant PP composite material, which is characterized in that specific production step are as follows:
(1) polystyrene, tetrahydrofuran and nano silica are stirred evenly, is put into electrostatic spinning apparatus and carries out spinning, obtains
To electrostatic spinning fiber, fibrous material is obtained for 24 hours in 80 DEG C of dryings;
(2) take wood powder and sodium hydroxide solution that 15min is mixed;
(3) it filters, and filter residue is rinsed with deionized water, rinse 3 ~ 5 times, by filter residue standing and drying, obtain modified wood powder;
(4) take nano-titanium dioxide, modified wood powder, calcium carbonate, EP rubbers, vinyltriethoxysilane and polysiloxanes mixed
It closes and uniformly obtains material A;
(5) polypropylene, dimethyl silicone polymer, maleic anhydride inoculated polypropylene is taken to be mixed to get material B;
(6) it takes material B to feed from twin-screw extrusion owner's spout, material A is taken to feed from side spout, twin-screw extrusion is female
Grain;
(7) master batch is put into 60 DEG C of warm water and stirs 30min, then master batch is filtered out and is put into 80 DEG C of vacuum drying ovens dry 2 ~ 4
Hour, by the master batch after drying by injection molding machine, obtain low odor scratch-resistant PP composite material.
2. a kind of preparation method of low odor scratch-resistant PP composite material as described in claim 1, which is characterized in that step
Suddenly the mass ratio of (1) described polystyrene, tetrahydrofuran and nano silica is 3:6:1.
3. a kind of preparation method of low odor scratch-resistant PP composite material as described in claim 1, which is characterized in that step
Suddenly (2) described concentration of sodium hydroxide solution is 3mol/L.
4. a kind of preparation method of low odor scratch-resistant PP composite material as described in claim 1, which is characterized in that step
Suddenly (4) described nano-titanium dioxide, modified wood powder, calcium carbonate, EP rubbers, vinyltriethoxysilane and polysiloxanes
Mass ratio is 20:20:20:15:1:10.
5. a kind of preparation method of low odor scratch-resistant PP composite material as described in claim 1, which is characterized in that step
Suddenly (5) described polypropylene, dimethyl silicone polymer, maleic anhydride inoculated polypropylene mass ratio be 100:20:1.
6. a kind of preparation method of low odor scratch-resistant PP composite material as described in claim 1, which is characterized in that step
Suddenly the mass ratio of (6) described material A and material B are 7:3.
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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EP1683836A1 (en) * | 2005-01-21 | 2006-07-26 | Mazda Motor Corporation | Thermoplastic elastomer composition for operating member and molded member obtained by molding the same |
CN102464830A (en) * | 2010-11-18 | 2012-05-23 | 上海杰事杰新材料(集团)股份有限公司 | Modified polypropylene material as well as preparation method and application thereof |
CN103627081A (en) * | 2012-08-22 | 2014-03-12 | 上海杰事杰新材料(集团)股份有限公司 | Wood plastic material and preparation method thereof |
CN106032421A (en) * | 2015-03-11 | 2016-10-19 | 株洲时代新材料科技股份有限公司 | A low-smell low-VOC flame-retardant automobile bellows and a preparing method thereof |
-
2018
- 2018-08-31 CN CN201811015027.2A patent/CN109280265A/en not_active Withdrawn
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1683836A1 (en) * | 2005-01-21 | 2006-07-26 | Mazda Motor Corporation | Thermoplastic elastomer composition for operating member and molded member obtained by molding the same |
CN102464830A (en) * | 2010-11-18 | 2012-05-23 | 上海杰事杰新材料(集团)股份有限公司 | Modified polypropylene material as well as preparation method and application thereof |
CN103627081A (en) * | 2012-08-22 | 2014-03-12 | 上海杰事杰新材料(集团)股份有限公司 | Wood plastic material and preparation method thereof |
CN106032421A (en) * | 2015-03-11 | 2016-10-19 | 株洲时代新材料科技股份有限公司 | A low-smell low-VOC flame-retardant automobile bellows and a preparing method thereof |
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Application publication date: 20190129 |